Fluoromethoxyacrylic acid derivatives and their use as pest control agents

ABSTRACT

The invention relates to new fluoromethoxyacrylic acid derivatives, a process for their preparation and their use as pesticides, as well as to new intermediates and a plurality of processes for their preparation. 
     It has already been disclosed that certain fluoromethoxyacrylic acid derivatives which are similar in constitution to the compounds described below have fungicidal properties (compare, for example, WO 9517376). The fungicidal action of these compounds, however, is unsatisfactory in many cases.

This application is a div. of Ser. No. 09/051,653 Apr. 16, 1998 U.S.Pat. No. 6,031,107 which is a 371 of PCT EP/96/04344 Oct. 7, 1996.

The invention relates to new fluoromethoxyacrylic acid derivatives, aprocess for their preparation and their use as pesticides, as well as tonew intermediates and a plurality of processes for their preparation.

It has already been disclosed that certain fluoromethoxyacrylic acidderivatives which are similar in constitution to the compounds describedbelow have fungicidal properties (compare, for example, WO 9517376). Thefungicidal action of these compounds, however, is unsatisfactory in manycases.

The new fluoromethoxyacrylic acid derivatives have now been found, ofthe general formula (I)

in which

Ar represents substituted aryl and

Q represents optionally substituted alkoxy.

Aryl represents aromatic, mono- or polycyclic hydrocarbon rings, suchas, for example, phenyl, naphthyl, anthranyl, phenanthryl, preferablyphenyl or naphthyl, in particular phenyl.

The compounds according to the invention, if appropriate, can exist asmixtures of various possible isomeric forms, in particular ofstereoisomers, such as, for example, E- and Z-. Both the E- and theZ-isomers, and also any desired mixtures of these isomers, are claimed.

The invention preferably relates to compounds of the formula (I), inwhich

Ar represents mono- to trisubstituted phenyl or optionally mono- totetrasubstituted naphthyl, the possible substituents preferably beingselected from the list below: halogen, cyano, nitro; alkyl, alkoxy,alkylthio, alkylsulphinyl or alkylsulphonyl, each of which isstraight-chain or branched and has 1 to 6 carbon atoms; alkenyl,alkenyloxy or alkinyloxy, each of which is straight-chain or branchedand has 2 to 6 carbon atoms; halogenoalkyl, halogenoalkoxy,halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl,each of which is straight-chain or branched and has 1 to 6 carbon atomsand 1 to 13 identical or different halogen atoms; halogenoalkenyl orhalogenoalkenyloxy, each of which is straight-chain or branched and has2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms;alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy,alkoxycarbonyl, alkylsulphonyloxy, hydroximinoalkyl or alkoximinoalkyl,each of which is straight-chain or branched and has 1 to 6 carbon atomsin the individual alkyl moieties; alkylene or dioxyalkylene, each having1 to 6 carbon atoms, and each of which is divalent and is optionallymono- or polysubstituted, identically or differently, by halogen and/orstraight-chain or branched alkyl having 1 to 4 carbon atoms and/orstraight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and1 to 9 identical or different halogen atoms; or cycloalkyl having 3 to 6carbon atoms, and

Q represents C₁-C₆-alkoxy which is optionally substituted by halogen orC₁-C₄-alkoxy.

In the definitions, the saturated or unsaturated hydrocarbon chains,such as alkyl, alkenyl or alkinyl, even linked to heteroatoms, such asin alkoxy, alkylthio or alkylamino, are each straight-chain or branched.

Halogen in general represents fluorine, chlorine, bromine or iodine,preferably fluorine, chlorine or bromine.

Cycloalkyl represents saturated, carbocyclic ring compounds, whichoptionally form a polycyclic ring system with other carbocyclic, fusedor bridged rings.

The invention relates in particular to compounds of the formula (I), inwhich

Ar represents phenyl which is mono- or disubstituted, identically ordifferently, the possible substituents preferably being selected fromthe list below: fluorine, chlorine, bromine, cyano, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, cyclopropyl, methoxy, ethoxy, n- ori-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl, trifluoromethyl,trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulphinylor trifluoromethylsulphonyl, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, ethoximinomethyl, methoximinoethyl, ethoximinoethyl,or methylenedioxy, ethylenedioxy, each of which is divalent and isoptionally mono- to tetrasubstituted, identically or differently, byfluorine, chlorine, methyl, trifluoromethyl or ethyl, and

Q represents methoxy or ethoxy.

The abovementioned radical definitions, given in general or in preferredranges, apply both to the final products of the formula (I) andcorrespondingly to the starting substances or intermediates needed ineach case for preparation.

These radical definitions can be combined with one another, i.e. alsobetween the given ranges of preferred compounds, in any desired manner.

It has furthermore been found that the fluoromethoxyacrylic acidderivatives of the formula (I) have very good microbicidal propertiesand can be employed for the protection of plants against harmfulorganisms.

Surprisingly, the substances according to the invention show a betteraction than constitutionally similar, previously known active compoundsof the same direction of action.

Finally, it has been found that both the new and the knownfluoromethoxyacrylic acid derivatives of the general formula (Ia)

in which

Ar¹ represents optionally substituted aryl and

Q¹ represents optionally substituted alkoxy,

are obtained when (process a) hydroxyaryl compounds of the generalformula (II)

in which

Q¹ has the meaning indicated above,

are reacted with a thiadiazole derivative of the general formula (III)

in which

Ar¹ has the meaning indicated above and

X represents halogen, alkylsulphonyl or arylsulphonyl,

if appropriate in the presence of an acid acceptor and if appropriate inthe presence of a diluent.

It is to be regarded as particularly surprising here that the processaccording to the invention proceeds with considerably higher yields thanthe process known according to the prior art.

In process a) according to the invention, preferably compounds of theformula (Ia) are prepared in which

Ar¹ represents phenyl which is optionally mono- to trisubstituted ornaphthyl which is optionally mono- to tetrasubstituted, the possiblesubstituents preferably being selected from the list below: halogen,cyano, nitro; alkyl, alkoxy, alkylthio, alkylsulphinyl oralkylsulphonyl, each of which is straight-chain or branched and has 1 to6 carbon atoms; alkenyl, alkenyloxy or alkinyloxy, each of which isstraight-chain or branched and has 2 to 6 carbon atoms; halogenoalkyl,halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl orhalogenoalkylsulphonyl, each of which is straight-chain or branched andhas 1 to 6 carbon atoms and 1 to 13 identical or different halogenatoms; balogenoalkenyl or halogenoalkenyloxy, each of which isstraight-chain or branched and has 2 to 6 carbon atoms and 1 to 11identical or different halogen atoms; alkylamino, dialkylamino,alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulphonyloxy,hydroximinoalkyl or alkoximinoalkyl, each of which is straight-chain orbranched and has 1 to 6 carbon atoms in the individual alkyl moieties;alkylene or dioxyalkylene, each having 1 to 6 carbon atoms, and each ofwhich is divalent and is optionally mono- or polysubstituted,identically or differently, by halogen and/or straight-chain or branchedalkyl having 1 to 4 carbon atoms and/or straight-chain or branchedhalogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical ordifferent halogen atoms or cycloalkyl having 3 to 6 carbon atoms; and

Q¹ represents C₁-C₆-alkoxy which is optionally substituted by halogen orC₁-C₄-alkoxy.

In particular, in process a) according to the invention, compounds ofthe formula (Ia) can be prepared in which

Ar¹ represents phenyl which is optionally mono- or disubstituted,identically or differently, the possible substituents preferably beingselected from the list below: fluorine, chlorine, bromine, cyano,methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl,methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- ori-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl orethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy,trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy,difluoromethylthio, trifluoromethylthio, difluorochloromethylthio,trifluoromethylsulphinyl or trifluoromethylsulphonyl, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl,ethoximinoethyl, or methylenedioxy, ethylenedioxy, each of which isdivalent and optionally mono- to tetrasubstituted, identically ordifferently, by fluorine, chlorine, methyl, trifluoromethyl or ethyl,and

Q¹ represents methoxy or ethoxy.

Formula (II) provides a general definition of the hydroxyaryl compoundsneeded as starting substances for carrying out process a) according tothe invention. In this formula (II), Q¹ preferably or in particular hasthe meaning which has already been indicated as preferred or asparticularly preferred in connection with the description of thecompounds of the formula (Ia) according to the invention.

The hydroxyaryl compounds of the formula (II) are still unknown; asnovel substances, they are a subject of the present application.

The hydroxyaryl compounds of the formula (II) are obtained (process b)when acetals of the formula (IV)

in which

R¹ represents alkyl,

R² represents hydrogen or alkyl or

R¹ and R², together with the atoms to which they are bonded, represent afive- or six-membered, heterocyclic ring

Q¹ has the meaning indicated above,

are hydrolysed at temperatures from −20° C. to 120° C., preferably attemperatures from −10° C. to 80° C., if appropriate in the presence of adiluent, preferably of an aliphatic, alicyclic or aromatic hydrocarbon,such as, for example, petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; of a halogenatedhydrocarbon, such as, for example, chlorobenzene, dichlorobenzene,dichloromethane, chloroform, tetrachloromethane, dichloroethane ortrichloroethane; of an ether, such as diethyl ether, diisopropyl ether,methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran,1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; of a ketone, such asacetone, butanone, methyl isobutyl ketone or cyclohexanone; of anitrile, such as acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile; of an ester such as methyl acetate or ethyl acetate; of asulphoxide, such as dimethyl sulphoxide; of a sulphone, such assulpholane; of an alcohol, such as methanol, ethanol, n- or i-propanol,n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol,ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether,diethylene glycol monoethyl ether, their mixtures with water or purewater, and if appropriate in the presence of an acid, preferably of aninorganic or organic protonic or Lewis acid, such as, for example,hydrochloric acid, sulphuric acid, phosphoric acid, formic acid, aceticacid, trifluoroacetic acid, methanesulphonic acid,trifluoromethanesulphonic acid, toluenesulphonic acid, boron trifluoride(also as etherate), boron tribromide, aluminium trichloride, zincchloride, iron(III) chloride, antimony pentachloride, or alternativelyof a polymeric acid such as, for example, an acidic ion exchanger, anacidic alumina or acidic silica gel.

Formula (IV) provides a general definition of the acetals needed asstarting substances for carrying out process b) according to theinvention. In this formula (IV), Q¹ preferably or in particular has themeaning which has already been indicated as preferred or as particularlypreferred for Q¹ in connection with the description of the compounds ofthe formula (Ia) according to the invention. R¹ represents alkyl,preferably methyl or ethyl, R² represents hydrogen or alkyl, preferablymethyl or ethyl, or R¹ and R², together with the atoms to which they arebonded, represent a five- or six-membered, heterocyclic ring, preferablytetrahydrofuryl or tetrahydropyrryl.

The acetals of the formula (IV) are still unknown; as new substancesthey are a subject of the present application.

The acetals of the formula (IV) are obtained when (process c) arylaceticacid derivatives of the formula (V)

in which

R¹, R² and Q¹ have the meanings indicated above,

are first reacted with a formic acid derivative, such as, for example,methyl formate, carbon monoxide, of a dialkylformamide acetal or of abis-dialkylaminoalkoxymethane, if appropriate in the presence of adiluent, preferably of an aliphatic, alicyclic or aromatic hydrocarbon,such as, for example, petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; of a halogenatedhydrocarbon, such as, for example, chlorobenzene, dichlorobenzene,dichloromethane, chloroform, tetrachloromethane, dichloroethane ortrichloroethane; of an ether, such as diethyl ether, diisopropyl ether,methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran,1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; of a ketone, such asacetone, butanone, methyl isobutyl ketone or cyclohexanone, of anitrile, such as acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile; of an ester such as methyl acetate or ethyl acetate; of anamide, such as N,N-dimethylformamide, N,N-dimethylacetamide,N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoramide; ofa sulphoxide, such as dimethyl sulphoxide; of a sulphone, such assulpholane; of an alcohol, such as methanol, ethanol, n- or i-propanol,n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol,ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether ordiethylene glycol monoethyl ether, and if appropriate in the presence ofa basic catalyst, preferably of an alkaline earth metal or alkali metalor ammonium hydride, hydroxide, amide, alkoxide, acetate, carbonate orhydrogen carbonate, such as, for example, sodium hydride, sodium amide,sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodiumhydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate,potassium acetate, calcium acetate, ammonium acetate, sodium carbonate,potassium carbonate, potassium hydrogen carbonate, sodium hydrogencarbonate or ammonium carbonate, or of a tertiary amine, such astrimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethyl-benzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU), attemperatures from −20° C. to 120° C., preferably at temperatures from−10° C. to 80° C., and the enols thus obtained of the formula (VI)

in which

R¹, R² and Q¹ have the meanings indicated above,

are reacted, preferably without further working up, withfluorobromomethane or fluorochloromethane, if appropriate in thepresence of a diluent, preferably of an aliphatic, alicyclic or aromatichydrocarbon, such as, for example, petroleum ether, hexane, heptane,cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; ofa halogenated hydrocarbon, such as, for example, chlorobenzene,dichlorobenzene, dichloromethane, chloroform, tetrachloromethane,dichloroethane or trichloroethane; of an ether, such as diethyl ether,diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; ofa ketone, such as acetone, butanone, methyl isobutyl ketone orcyclohexanone; of a nitrile, such as acetonitrile, propionitrile, n- ori-butyronitrile or benzonitrile; of an ester such as methyl acetate orethyl acetate; of an amide, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoramide; of a sulphoxide, such as dimethyl sulphoxide;of a sulphone, such as sulpholane; of an alcohol, such as methanol,ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol,propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, their mixtures withwater or pure water, and if appropriate in the presence of a base,preferably of an alkaline earth metal or alkali metal or ammoniumhydride, hydroxide, amide, alkoxide, acetate, carbonate or hydrogencarbonate, such as, for example, sodium hydride, sodium amide, sodiummethoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide,potassium hydroxide, ammonium hydroxide, sodium acetate, potassiumacetate, calcium acetate, ammonium acetate, sodium carbonate, potassiumcarbonate, potassium hydrogen carbonate, sodium hydrogen carbonate orammonium carbonate, or of a tertiary amine, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethyl-benzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU), attemperatures from −20° C. to 120° C., preferably at temperatures from−10° C. to 80° C.

Formula (V) provides a general definition of the arylacetic acidderivatives needed as starting substances for carrying out process c)according to the invention for the preparation of the acetals of theformula (IV). In this formula (V), Q¹ preferably or in particular hasthe meaning which has already been indicated as preferred or asparticularly preferred for Q¹ in connection with the description of thecompounds of the formula (Ia) according to the invention. R¹ and R²preferably have those meanings which have already been indicated aspreferred in connection with the description of the compounds of theformula (IV).

The arylacetic acid derivatives of the formula (V) are known in somecases and/or can be prepared by known processes (compare, for example,J. Org. Chem. 1994, 203-13).

Arylacetic acid derivatives which are new and also a subject of thepresent application are those of the formula (Va)

in which

R³ and R⁴ are identical or different and independently of one anotherrepresent alkyl and

Q¹ has the meaning indicated above.

The arylacetic acid derivatives of the formula (Va) are obtained(process d) when hydroxy compounds of the general formula (VII)

in which

Q¹ has the meaning indicated above,

are reacted with vinyl ethers of the general formula (VIII)

in which

R³ has the meaning indicated above and

R⁵ represents hydrogen or alkyl,

if appropriate in the presence of a diluent, preferably of an aliphatic,alicyclic or aromatic hydrocarbon, such as, for example, petroleumether, hexane, heptane, cyclohexane, methylcyclohexane, benzene,toluene, xylene or decalin; of a halogenated hydrocarbon, such as, forexample, chlorobenzene, dichlorobenzene, dichloromethane, chloroform,tetrachloromethane, dichloroethane or trichloroethane; of an ether, suchas diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amylether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethaneor anisole, or of a nitrile, such as acetonitrile, propionitrile, n- ori-butyronitrile or benzonitrile, and if appropriate in the presence ofan acid, preferably of an inorganic or organic protonic or Lewis acid,or alternatively of a polymeric acid, such as, for example, hydrochloricacid, sulphuric acid, phosphoric acid, formic acid, acetic acid,trifluoroacetic acid, methanesulphonic acid, trifluoromethanesulphonicacid, toluenesulphonic acid, boron trifluoride (also as etherate), borontribromide, aluminium trichloride, zinc chloride, iron(III) chloride,antimony pentachloride, acidic ion exchangers, acidic aluminas andacidic silica gel.

Formula (Va) provides a general definition of the new arylacetic acidderivatives. In this formula (Va), Q¹ preferably or in particular hasthose meanings which have already been indicated as preferred or asparticularly preferred for Q¹ in connection with the description of thecompounds of the formula (la) according to the invention. R³ and R⁴ areidentical or different and independently of one another represent alkyl,preferably methyl or ethyl.

Formula (VII) provides a general definition of the hydroxy compoundsneeded for carrying out process d) according to the invention for thepreparation of the compounds of the formula (Va) according to theinvention. In this formula (VII), Q¹ preferably or in particular has themeaning which has already been indicated as preferred or as particularlypreferred for Q¹ in connection with the description of the compounds ofthe formula (Ia) according to the invention.

The hydroxy compounds of the formula (VII) are known synthesischemicals.

Formula (VIII) provides a general definition of the vinyl ethersfurthermore needed for carrying out process d) according to theinvention for the preparation of the compounds of the formula (Va)according to the invention. In this formula (VIII), R³ preferably hasthe meaning which has been indicated as preferred or as particularlypreferred for R³ in connection with the description of the compounds ofthe formula (Va) according to the invention. R⁵ represents hydrogen oralkyl, preferably hydrogen or methyl.

The vinyl ethers of the formula (VIII) are known synthesis chemicals.

Formula (III) provides a general definition of the thiadiazolederivatives furthermore needed as starting substances for carrying outprocess a) according to the invention. In this formula (III), Ar¹preferably or in particular has the meaning which has already beenindicated as preferred or as particularly preferred for Ar¹ inconnection with the description of the compounds of the formula (Ia)according to the invention. X represents halogen, preferably fluorine orchlorine, or alkylsulphonyl or arylsulphonyl, preferablymethylsulphonyl, benzylsulphonyl or tolylsulphonyl.

The thiadiazole derivatives of the formula (III) are known synthesischemicals and/or can be prepared by known processes (compare, forexample, J. Heterocyclic Chem. 30, 357 (1993)).

All inert organic solvents are suitable as diluents for carrying outprocess a) according to the invention. These preferably includealiphatic, alicyclic or aromatic hydrocarbons, such as, for example,petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane,benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as,for example, chlorobenzene, dichlorobenzene, dichloromethane,chloroform, tetrachloromethane, dichloroethane or trichloroethane;ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether,methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; ketones, such as acetone, butanone,methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile,propionitrile, n- or i-butyronitrile or benzonitrile; amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoramide; esters such as methylacetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide;sulphones, such as sulpholane; alcohols, such as methanol, ethanol, n-or i-propanol, n-, i-, sec- or tert-butanol, ethanediol,propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, mixtures thereofwith water or pure water.

Process a) according to the invention is optionally carried out in thepresence of a suitable acid acceptor. Those possible are all customaryinorganic or organic bases. These include, for example, alkaline earthmetal or alkali metal or ammonium hydrides, hydroxides, amides,alkoxides, acetates, carbonates or hydrogen carbonates, such as, forexample, sodium hydride, sodium amide, sodium methoxide, sodiumethoxide, potassium tert-butoxide, sodium hydroxide, potassiumhydroxide, ammonium hydroxide, sodium acetate, potassium acetate,calcium acetate, ammonium acetate, sodium carbonate, potassiumcarbonate, potassium hydrogen carbonate, sodium hydrogen carbonate orammonium carbonate, and also tertiary amines, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethyl-benzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out process a) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the reaction is carried out at temperatures from 0° C. to 150° C.,preferably at temperatures from 0° C. to 80° C.

To carry out process a) according to the invention for the preparationof the compounds of the formula (Ia), in general 0.2 to 5 mol,preferably 0.5 to 2 mol, of thiadiazole derivative of the generalformula (III) are employed per mole of the hydroxyaryl compounds of thegeneral formula (II).

Process a) according to the invention is in general carried out undernormal pressure. However, it is also possible to work at elevated orreduced pressure—in general between 0.1 bar and 10 bar.

The reaction is carried out and worked up, and the reaction products areisolated by known processes (cf. also the Preparation Examples).

The active compounds according to the invention have a potentmicrobicidal action and can be employed in practice for controllingundesired microorganisms. The active compounds are suitable for use asplant protection agents, in particular as fungicides.

Fungicidal agents are employed in plant protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, ZygomycetesAscomycetes, Basidiomycetes and Deuteromycetes.

Bactericidal agents are employed in plant protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as examples, butnot by way of limitation:

Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Altemaria brassicae; and

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for controlling plant diseases, permitstreatment of above-ground parts of plants, of vegetative propagationstock and seeds, and of the soil.

The active compounds according to the invention can be employed here toparticularly good effect for controlling cereal diseases, such as, forexample, against Erysiphe or Leptosphaeria species, or diseases inviticulture, fruit- and vegetable growing, such as, for example, againstPlasmopara, Uncinula, Sphaerotheca or Venturia species, or alternativelyrice diseases, such as, for example, Pyricularia species. The activecompounds according to the invention additionally show a particularlypotent and wide in vitro action.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, very fine capsules in polymeric substances and in coatingcompositions for seed, as well as ULV cold mist and warm mistformulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at ambient temperature andunder atmospheric pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, argillaceous earths, talc, chalk,quartz, attapulgite, montmorillonite or diatomaceous earth, and groundsynthetic minerals, such as highly-disperse silica, alumina andsilicates; as solid carriers for granules there are suitable: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, as well as synthetic granules ofinorganic and organic meals, and granules of organic material such assawdust, coconut shells, maize cobs and tobacco stalks; as emulsifyingand/or foam-forming agents there are suitable: for example non-ionic andanionic emulsifiers, such as polyoxyethylene fatty acid esters,polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycolethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well asalbumen hydrolysis products; as dispersing agents there are suitable:for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in theirformulations, can also be used as a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, for example towiden the spectrum of action or to prevent the build-up of resistance.In many cases, synergistic effects are obtained, i.e. the activity ofthe mixture is greater than the activity of the individual components.

Synergistic actions are observed here in many cases.

Examples of particularly advantageous mixture components are thefollowing compounds:

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide;8-hydroxyquinoline sulphate; methyl(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate, calciumpolysulphide, captafol, captan, carbendazim, carboxin, quinomethionate,chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazol,diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole,dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine,dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos,epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole,fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentinacetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil,fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole,furalaxyl, furmecyclox, guazatine, hexachlorobenzene, hexaconazole,hymexazol, imazalil, imibenconazole, iminoctadine, iprobenfos (IBP),iprodione, isoprothiolane, kasugamycin, copper preparations such as:copper hydroxide, copper naphthenate, copper oxychloride, coppersulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper,mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole,methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron,phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz,procymidone, propamocarb, propiconazole, propineb, pyrazophos,pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB), sulphur andsulphur preparations, tebuconazole, tecloftalam, tecnazene,tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram,tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide,trichlamide, tricyclazole, tridemorph, triflumizole, triforine,triticonazole, validamycin A, vinclozolin, zineb, ziram

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furanecarboxylic acid, oxytetracyclinprobenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,azocyclotin, Bacillus thuringiensis,4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile,bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, bifenthrin, BPMC,brofenprox, bromophos A, bufencarb, buprofezin, butocarboxin,butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion,carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos,N-[(6-chloro-3-pyridinyl)-methyl]-N′-cyano-N-methyl-ethaneimidamide,chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine,cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyromazine, deltamethrin, demeton-M, demeton-S,demeton-S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos,dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate,dimethylvinphos, dioxathion, disulfoton, edifenphos, emamectin,esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos,etofenprox, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide,fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin,fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flufenprox,fluvalinate, fonophos, formothion, fosthiazate, fubfenprox,furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox, imidacloprid,iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin,lambda-cyhalothrin, lufenuron, malathion, mecarbam, mevinpbos,mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion,methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,naled, NC 184, nitenpyram, omethoate, oxamyl, oxydemethon M,oxydeprofos, parathion A, parathion M, permethrin phenthoate, phorate,phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos,prothoate, pymetrozin, pyrachlophos, pyraclofos, pyrachlophos,pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen,pyriproxifen, quinalphos, salithion, sebufos, silafluofen, sulfotep,sulprofos, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron,tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox,thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin,tralomethrin, triarathen, triazophos, triazuron, trichlorfon,triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, YI 5301/5302,zetamethrin.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators is also possible.

The active compounds according to the invention are used as such or inthe form of their commercially available formulations or the use formsprepared therefrom, such as ready-to-use solutions, suspensions,wettable powders, pastes, soluble powders, dusts and granules. They areused in the customary manner, for example by watering, spraying,atomizing, scattering, foaming, brushing on and the like. It isfurthermore possible to apply the active compounds by the ultra-lowvolume method or to inject the active compound preparation or the activecompound itself into the soil. The seeds of the plants can also betreated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001% by weight.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

PREPARATION EXAMPLES Example 1

Process a)

A solution of 3.2 g (0.005 mol) of3-phenyl-5-methanesulphonyl-1,2,4-thiadiazole and 2.3 g of methyl2-(2-hydroxyphenyl)-3-fluoromethoxy-acrylate in 10 ml of drydimethylformamide is treated at 0° C. with 0.2 g (0.005 mol) of 80%strength sodium hydride in mineral oil. The mixture is stirred for 4hours at this temperature, and for a further 18 hours without cooling,and then concentrated. The residue is taken up using ethyl acetate, thesolution is washed with water, and the organic phase is dried oversodium sulphate and concentrated again. The crude product ischromatographed on silica gel using hexane/acetone (7:3). 1.3 g (67% oftheory) of methyl2-[2-(3-phenyl-1,2,4-thiadiazol-5-yloxy)-phenyl]-3-fluoromethoxy-acrylateare obtained as a yellow, highly viscous oil.

¹H-NMR (CDCl₃, TMS): δ=5.4 (d, 2H) ppm.

Example 2

Process a)

A solution of 3.2 g (0.01 mol) of3-phenyl-5-toluenesulphonyl-1,2,4-thiadiazole and 1.1 g of methyl2-(2-hydroxyphenyl)-3-fluoromethoxy-acrylate in 30 ml of drydimethylformamide is treated at 0° C. with 0.3 g (0.01 mol) of 80%strength sodium hydride in mineral oil. The mixture is stirred for 3days without cooling and then concentrated. The residue is taken upusing ethyl acetate, the solution is washed with water, and the organicphase is dried over sodium sulphate and concentrated again. The crudeproduct is chromatographed on silica gel using hexane/acetone (9:1). 2.8g (60% of theory) of methyl2-{2-[3-(4-bromophenyl)-1,2,4-thiadiazol-5-yloxy]-phenyl}-3-fluoromethoxy-acrylateare obtained as a yellow, highly viscous oil.

¹H-NMR (CDCl₃, TMS): δ=5.4 (d, 2H) ppm.

Preparation of the Starting Substance Example II-1

Process b)

6.2 g (0.02 mol) of methyl2-[2-(tetrahydropyran-2-yloxy)-phenyl]-3-fluoromethoxy-acrylate arestirred in 30 ml of methanol at 20° C. for 18 hours with 0.5 g of acidicion exchanger. The ion exchanger is filtered off and the filtrate isconcentrated. The residue is chromatographed on silica gel usinghexane/acetone (7:3). 3.3 g (73% of theory) of methyl2-(2-hydroxyphenyl)-3-fluoromethoxy-acrylate are obtained as a paleyellow, viscous oil.

¹H-NMR (CDCl₃, TMS): δ=5.4 (d, 2H) ppm.

Ethyl 2-(2-hydroxyphenyl)-3-fluoromethoxy-acrylate is also obtainedanalogously to Example II-1 and corresponding to the general descriptionof preparation process b) according to the invention.

¹H-NMR (CDCl₃, TMS): δ=1.30 (t, 3H); 4.32 (q, 2H) ppm.

Preparation of the Precursor Example IV-1

Process c)

1.5 g of 80% strength sodium hydride in mineral oil are added inportions at 20° C. with stirring to a solution of 12.5 g (60 mmol) ofmethyl 2-[2-(tetrahydropyran-2-yloxy)-phenyl]-acrylate and 30 g ofmethyl formate in 150 ml of dry dimethylformamide in a three-neckedflask having an attached condenser. After approximately one hour, theexothermic reaction commences with foaming. The temperature is kept at40° C. for 3 hours. The mixture is cooled to 0-5° C. and treatedsuccessively with 4.8 g (0.05 mol) of methanesulphonic acid and inportions with 13.8 g (0.1 mol) of potassium carbonate. The temperatureof the cooling fluid in the condenser, as well as the temperature of thereaction mixture, is then adjusted to 0° C. Using a syringe, 6.8 g (0.06mol) of bromofluoromethane are added and the mixture is stirredovernight at 0-5° C. The reaction mixture is stirred for a further 24hours without cooling. The temperature of the cooling fluid is kept atapproximately 0° C. The mixture is concentrated, the residue is taken upusing ethyl acetate, the solution is washed with water, and the organicphase is dried over sodium sulphate and concentrated again. The residueis chromatographed on silica gel using hexane/acetone (7:3). 11.6 g (75%of theory) of methyl2-[2-(tetrahydropyran-2-yloxy)-phenyl]-3-fluoromethoxy-acrylate areobtained.

¹H-NMR (CDCl₃, TMS): δ=5.5 (d, 2H) ppm.

The compounds of the formula (Ia) according to the invention, shown inTable 1 below, are also obtained analogously to Examples (1-2), andcorresponding to the general description of the preparation processaccording to the invention:

TABLE 1

Ex.- No. Ar¹ Q¹ Physical data Isomers  3

—OCH₃ NMR: 5.4 (d, 2H) E-isomer  4

—OCH₃ NMR: 5.3 (d, 2H) E-isomer  5

—OCH₃ NMR: 5.3 (d, 2H) E-isomer  6

—OCH₃ NMR: 5.3 (d, 2H) E-isomer  7

—OCH₃ NMR: 5.3 (d, 2H) E-isomer  8

—OCH₃ NMR: 5.3 (d, 2H) E-isomer  9

—OCH₃ E-isomer 10

—OCH₃ E-isomer 11

—OC₂H₅ NMR: 5.42 (d, 2H); 7.63 (s, 1H) E-isomer 12

—OC₂H₅ NMR: 5.42 (d, 2H); 7.65 (s, 1H) E-isomer 13

—OCH₃ E-isomer 14

—OCH₃ E-isomer 15

—OCH₃ E-isomer 16

—OC₂H₅ NMR: 5.39 (d, 2H); 7.65 (s, 1H) E-isomer 17

—O—CH₃ NMR: 5.40 (d, 2H); E-isomer 18

—O—CH₃ NMR: 5.40 (d, 2H); E-isomer 19

—OCH₃ NMR: 5.40 (d, 2H); E-Isomer 20

—OCH₃ ¹H-NMR: 5.5 (d, 2H); Z-isomer 21

—OCH₃ ¹H-NMR: 5.5 (d, 2H); Z-isomer 22

—OCH₃ Fp: 113° C. Z-isomer 23

—OCH₃ ¹H-NMR: 5.4 (d, 2H); E-isomer

USE EXAMPLES Example: A

Plasmopara Test (Vine)/Protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound. After the spray coating has dried on,the plants are inoculated with an aqueous spore suspension of Plasmoparaviticola and then remain in a humidity chamber at 20 to 22° C. and 100%relative atmospheric humidity for 1 day. The plants are then placed in agreenhouse at 21° C. and about 90% atmospheric humidity for 5 days. Theplants are then moistened and placed in a humidity chamber for 1 day.

Evaluation is carried out 6 days after the inoculation.

In this test, for example, the following compound (2) of the PreparationExamples shows an efficacy of 100% at an active compound concentrationof 100 ppm.

TABLE A Efficacy in % of the untreated control at Plasmopara test(vine)/protective an active compound concentration of Active compound100 ppm

100 (2) (according to the invention)

Example: B

Uncinula Test (Vine)/Protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound. After the spray coating has dried on,the plants are dusted with conidia of the fungus Uncinula necator. Theplants are then placed in a greenhouse at 23 to 24° C. and a relativeatmospheric humidity of about 75%.

Evaluation is effected 14 days after the inoculation.

In this test, for example, the following compound (2) of the PreparationExamples shows an efficacy of 100% at an active compound concentrationof 10 ppm.

TABLE B Efficacy in % of the untreated control at Uncinula test(vine)/protective an active compound concentration of Active compound 25ppm

100 (2) (according to the invention)

Example: C

Sphaerotheca Test (Cucumber)/Protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound. After the spray coating has dried on,the plants are dusted with conidia of the fungus Sphaerotheca fuliginea.

The plants are then placed in a greenhouse at 23 to 24° C. and at arelative atmospheric humidity of about 75%.

Evaluation is carried out 10 days after the inoculation.

In this test, for example, the following compound (2) of the PreparationExamples shows an efficacy of 100% at an active compound concentrationof 100 ppm.

TABLE C Efficacy in % of the untreated control at Sphaerotheca test(cucumber)/protective an active compound concentration of Activecompound 100 ppm

100 (2) (according to the invention)

Example D

Venturia Test (Apple)/Protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound. After the spray coating has dried on,the plants are inoculated with an aqueous conidia suspension of theapple scab causative organism Venturia inaequalis and then left in anincubation cabin at 20° C. and 100% relative atmospheric humidity for 1day.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, for example, the following compound (2) of the PreparationExamples shows an efficacy of 100% at an active compound concentrationof 10 ppm.

TABLE D Efficacy in % of the untreated control at Venturia test(apple)/protective an active compound concentration of Active compound10 ppm

100 (2) (according to the invention)

Example E

Erysiphe Test (Barley)/Protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at given application rate.

After the spray coating has dried on, the plants are dusted with sporesof Erysiphe graminis f.sp. hordei.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, for example, the following compound (2) shows an efficacyof 81% at an active compound application rate of 250 g/ha.

TABLE E Efficacy in % of the untreated control at Erysiphe test(barley)/protective an active compound concentration of Active compound250 g/ha

81 (2) (according to the invention)

Example F

Leptosphaeria nodorun Test (Wheat)/Protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound.

After the spray coating has dried on, the plants are sprayed with aspore suspension of Leptosphaeria nodorum. The plants remain for 48hours in an incubation cabin at 20° C. and 100% relative atmospherichumidity.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is effected 10 days after the inoculation.

In this test, for example, the following compound of the PreparationExamples (2) shows an efficacy of 88% at an active compound applicationrate of 250 g/ha.

TABLE F Efficacy in %, relative to the untreated Leptosphaeria nodorumtest (wheat)/protective control, at an active compound Active compoundapplication rate of 250 g/ha

88 (2) (according to the invention)

What is claimed is:
 1. A compound of the formula (II):

in which Q¹ represents unsubstituted or substituted alkoxy.
 2. A processfor preparing a compound of the formula (II) according to claim 1, saidprocess comprising hydrolyzing an ether compound of the formula:

in which R¹ represents alkyl; and R² represents hydrogen or alkyl; or R¹and R², together with the atoms to which they are bonded, represent afive- or six-membered heterocyclic ring; and Q¹ represents unsubstitutedor substituted alkoxy; at a temperature from −20° C. to 120° C.,optionally in the presence of a diluent, and optionally in the presenceof an acid.
 3. An ether compound of the formula:

in which R¹ represents alkyl; and R² represents hydrogen or alkyl; or R¹and R², together with the atoms to which they are bonded, represent afive- or six-membered heterocyclic ring; and Q¹ represents unsubstitutedor substituted alkoxy.
 4. A process for preparing an ether compoundaccording to claim 3, said process comprising: a) reacting an arylaceticacid derivative of the formula:

 in which R¹ represents alkyl; and R² represents hydrogen or alkyl; orR¹ and R², together with the atoms to which they are bonded, represent afive- or six-membered heterocyclic ring; and Q¹ represents unsubstitutedor substituted alkoxy; with a formic acid derivative of adialkylformamide acetal or of a bis-dialkylaminoalkoxymethane at atemperature from −20° C. to 120° C., optionally in the presence of adiluent, and optionally in the presence of a basic catalyst, to form anenol of the formula:

 in which R¹, R² and Q¹ have the meanings indicated above; and b)reacting said enol with fluorobromomethane or fluorochloromethane at atemperature from −20° C. to 120° C., optionally in the presence of adiluent, and optionally in the presence of a base.
 5. The processaccording to claim 4, wherein steps a) and/or b) are carried out at atemperature from −10° C. to 80° C.
 6. The process according to claim 4,wherein step b) is conducted after step a) without further working up.7. A process for preparing a compound of the formula (Ia):

in which Ar¹ represents unsubstituted or substituted aryl; and Q¹represents unsubstituted or substituted alkyl; said process comprising:a) reacting an arylacetic acid derivative of the formula:

 in which R¹ represents alkyl; and R² represents hydrogen or alkyl; orR¹ and R², together with the atoms to which they are bonded, represent afive- or six-membered heterocyclic ring; and Q¹ has the meaningindicated above; with a formic acid derivative of a dialkylformamideacetal or of a bis-dialkylaminoalkoxymethane at a temperature from −20°C. to 120° C., optionally in the presence of a diluent, and optionallyin the presence of a basic catalyst, to form an enol of the formula:

in which R¹, R² and Q¹ have the meanings indicated above; and b)reacting said enol with fluorobromomethane or fluorochloromethane at atemperature from −20° C. to 120° C., optionally in the presence of adiluent, and optionally in the presence of a base, to yield an ethercompound of the formula:

 in which R¹, R² and Q¹ have the meanings indicated above; c)hydrolyzing said ether compound at a temperature from −20° C. to 120°C., optionally in the presence of a diluent, and optionally in thepresence of an acid, to form a compound of the formula (II):

 and d) reacting said compound of the formula (II) with a thiadiazolecompound of the formula (III):

 in which Ar¹ has the meaning indicated above; and X represents halogen,alkylsulphonyl or arylsulphonyl; optionally in the presence of an acidreceptor, and optionally in the presence of a diluent, to form saidcompound of the formula (Ia).